Azo dyestuffs insoluble in water and fiber dyed therewith



Patented June 20, 1939 PATENT OFFICE AZO DYESTUFFS INSOLUBLE IN WATER AND FIBER DYED THEREWITH Erwin Thoma, Frankfort-on-the-Main-Hochst,

and Wilhelm Seidenfaden, Ofienbach-on-the- Main, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application March 23, 1937, Se-

rial No. 132,648.

10 Claims.

The present invention relates to azo-dyestufis insoluble in water and to fiber dyed therewith; more particularly it relates to dyestuffs of the following general formula:

wherein the azo-groups stand in para-position to each other, R and R1 stand for radicals of the benzene or naphthalene series, X1 stands for a member of the group consisting of alkyl OO.N(elky1)z, CO.N

alkyl -s Oz.N(a1kyl) and s OZ-N CaHs fXzmeans halogen, a nitro or cyano group, X3v hydrogen, halogen or alkoxy and Z hydrogen,

"halogen or alkoxy.

azo-dyestufis are obtainable by coupling an -arylide of an ortho-hydroxy-aryl-carboxy1ic acid .orbeta-ketocarboxylic acid with a diazo-compolmidifrom a para-amino-azo-compound of the benzene or naphthalene series corresponding with the following general formula:

wherein the amino-group stands in para-position to the azo-group, R stands for a radical of the member of the group consisting of alkyl O0.N(alkyl)z, CO.N

CuHs

alkyl -S0z.N(alkyl)2 and SOz.N

' CuHa We have found that valuable water-insoluble benzene or naphthalene series, X1 stands for a In Germany April 2, 1936 X2 means halogen, a nitro or cyano group, and X2 hydrogen, halogen or alkoxy; the dyestuif components must not contain any group which lends solubility, for instance a sulfonic or carboxylic acid group. The dyestuffs may be made in substance, on a fiber or on a substratum adaptdyestufi on the fiber in printing a material concentrated printing pastes are obtainable. In

producing the dyestuff on yarn there may be added to the diazo-salt solution a salt, as is the case with the diazotized amines of the benzene series.

Furthermore, in the case of the diazonium com- I pounds of the aforesaid kind, there is frequently tobe noticed the property, important for the making of the dyestuffs, that the mineral acid diazo-salt solutions are little sensitive to the addition of buffer agents, as for example sodium acetate. This very favorable property makes it possible, after the production of the dyestufi, to wash out easily non-coupled portions of diazonium salt. Many combinations do not bleed yellow in the washing sample and thus do not show a defect which is frequently to be observed in the combinations from diazotized 4-aminoazo-compounds which are frequently used in practice. Other combinations are of high fastness to light.

The new dyestufis are of veryv various tints. Thus, by using arylides of beta-ketocarboxylic acids there are obtained on the fiber orange-red, orange-brown, bluish-red, Bordeaux-red and brown-red tints which in part cannot be obtained with the already known para-aminoazo-compounds. With the arylides of ortho-hydroxycarbazole-carboxylic acids there may be obtained for example, currant tints of high fastness to light. Further, fine black tints are obtained which in part are essentially faster to light than the dyeings obtainablefrom known para-aminoazo-compounds. By using 2,3-hydroxynaphthoic acid-arylides, there are obtained, for example Bordeaux, currant, garnet, navy blue and greenish-blue, blue-black, black-violet and deep grey tints which in many cases are distinguished by a high fastness to light and good fastness to washing and chlorine.

position which they have in the para-aminoazo body of the benzene or naphthalene series. Further, the presence of other substituents such as alkyl-, alkoxyor nitro-groups and halogen is of importance. V

The following examples serve to illustrate the invention, but they are not intended to limitit thereto:

1. 50 grams of cotton yarn are treated withl l good fastness to washing'and chlorine and of goodfastness to light. Thedy'estuff corresponds with the following formula:

pyrophosphate and sodium bicarbonate is added to the grounding bath.

If instead of the grounding recommended above, 4.5 grams of 1-(2',3'-hydroxynaphthoylamino)-2A-dimethoxy-5-chlorobenzene are used, 5 there is also obtained a dark blue of good fastness to washing and chlorine. By using 3.5 grams l (2' ,3 -hydroxynaphthoylamino) -naphthalene, there is obtained a dull greenish-blue.

"Instead of using the separated zinc-chloride 0 double salt of the diazonium chloride there may be used the easily obtainable diazo-solution from the amine itself bydiazotizing 3.7 grams of the base in 4 cc. of hydrochloric acid of 30 per cent.

strength with the addition of iced water by means 15 of a solution of 0.7 gram of sodium nitrite and making up to 1 liter with a solution of 3 grams of sodium acetate with addition of a solution of 40 grams of sodium chloride.

2. The goods are grounded with 6.3 grams of )1- (2',3'-hydroxynaphthoylamino) 2 -methylben- 'zene and developed'with a diazo-solution from 3.6 grams of 2-methoxy-5-methyl -4-nitro-2- OCH:

NO N=N N: --l

CO.N(CH:)2 CH: 0H

The azo-dyestufi may also be produced on other carboxylic 'ac1d-dimethyl-amidel-aminoazobenfibers than on cotton. There 15, for instance, zene. There is obtained a very deep dark blue of obtained a dark blue on yarn from a mixture very good fastness to light. of spun rayon and wool 1f the yarn is pre- The following table indicates a number of other bleached with hydrogen peroxide and sodium azo-dyestuffs obtamable by the 1nvent1on:-- 40 Blaze-components Coupling components Color tints V 1-(2,3'-hydroxynaphthoyl-amino)-- '4 amino-2-methyl-5-meth0xy-2-carboxylic' ecid-diethylamide- -2,5-dimethoxy-4-cblorobenzene Dark blue.

4 -nitro-azobenzene.

o (10---, Greenish dark blue. i-amino-2-methyl-5-meth0xy-2 -'carboxylic acid dimethyl -4-methoxybenzene Dull greenishblue. amider i nitro-azobenzene. 7 I p 7 f V i i V 4-amino-2-methoxy-5-methyl 2 carboxylic acid -"dimethyl -2-methoxybenzene Very deep dull blue.

amide-4-nitro-azobenzene.

Do--- benzene Deep dark blue. Do--- -2,5- d methoxybenzene Verydull deep blue. Do--. -2,5-d1meth0xy-4-chlorobenzene Currant. 4-amino-2-metl1oxy-5-metl1yl-2-carboxylic acid-diethylamide- -4 -chlorobenzene A. Greenish dull blue.

4-nitro-azobenzene.

-benzene Dark blue. -2-methylbenzene Do. -4-metboxybenzene Blue-black -2- methyl-4-methoxybenzene Reddish black. -3-methyl-4-metl1oxybenzcne Rcddish blue-black. -2.5-dimethoxybenzene Reddishblue. 4-amino-2, imethoxy-2-carboxylic acid-diethyl-amide-3- -2,5-dimethoxy-4-chlorobenze Blue-black.

chloro-azobenzene. 4-emino-2,5-dimethoxy-2-carboxy1ic acid-diethyl-amide-4'- -2-methyl4-methoxybenzene Very dull blue. chloro-azobenzene.

4-amino-2.S-dimethoxy-W-carboxylic 'acid-diethyl-amide-5- -3-nltrobenzene Blue-black. 1

- chloro-azobenzene. 4-amino-2,5-dimethoxy-3-carboxylic acid-diethyl-amidei -4-methoxybenzene Reddish dark blue.

ehloro-azobenzene. Do -2,4dimethoxy-fi-chlorobenzene Black-blue. 4-amino-2,5-dimethoxy-3-carboxyl1c acid-diethyl-amide-fi- -2-methyl-*i-metboxmbenzene Very reddish dark chloro-azobenzene. blue. 4-amino-2,5-dimethoxy-4-carboxy1ic acid-diethyl-amide- -2,fi-dimethoxy-i-cl lorobenzene Very deep blue.

chloro-azobenzene. w 1-65 4-amino-2,5 dimethoxy-2-carboxylic acid-dimethyl-amide4- -2-methyl-4-methoxybenzene Greenish darkiblue.

nitto'azobenzene.

Dn -2-methylbenzene Greenish black. Dn -2-methoxybenzene Do. I D -2,5-dimethoxybenzene Do. 4-aminc-2,5-dimethoxy-2-carboxylic acid-diethyl-amide-4'- -2,5-dimethoxy-i-chlorobenzene Dark blue.

mtro-azobenzene.

n -benzene Greenish black-blue. Do -2-methylbenzene Do. Do -2-methoxybenzene Greenish blue-black. D -2-methyl-4-methoxy-benzene Do. D I -2,5-dimethoxybenzene Do. 1 H r e 2-(2,3-hydroxynaphthoylarnino) I 4-an ino-2,5 d1methoxy-2'-carboxylic acid-N-methyl-anilide- -naphthalene Dark blue.

4-nitro-azobe1izene.

Diazo-components Coupling components Color tints 1-(2,3-hydroxynaphthoylamino) 4-amrn0-2,5-d1methoxy-2f-carboxyl1c acid-N-methyl-anilide- 4- -benzene Blue-black. nitro-azobe'nzene. 7 r D -2-methylbenzene Do. D -4-methoxybenzene Do.- Do -2-methyl-i-methoxybenzene. Do. D -2-rnethoxy-5-chlorobenzene Do. I?" I j -2,5dimethxybenzene D0. r 4-am1no-2,5-d1ethoxy-2-carboxyhc acid-di-methylamide 4-ni- -benzene Dull greenish blue.

tro-azobenzenep I 1 l y i-amilno-2,fi-diethoW-T-carbcxylic acid-di-ethylamidei-nitro- -2-methy1benzene Middle blue.

8.20 91129118. 4 amino- 1 (ortho carboxylic acid diethylamide para -2,4-dimethoxy-5-chlorobenzene Currant.

nitro-phenylazo) -5,6,7,8-tetrahydronaphthalene. 4- amino l (ortho carboxylic aciddiethylamide para -nitr0 pheny1azo)-naphthalene. 4-amino-2-methyl-5-methoxy-2'-nitro-4-sulfonic acid-dimethylamide-azobenzene. 4-8mino-2-mcthyl-5-meth0xy-2'-su1f0nic acid-dietli'yl'amide-4- ni%o-azobenzene.

D0 4-amino-2-methyl-5-ethoxy2-suhonic acid-diethylamide-4'-nitro-azobenzene.

Do D0 4-amino-2-methyl-5-ethoxy-2-chl0ro-4Gnitro-6-su1fonic aci methyl-amide-azobenzene.

Do 4-amino-2,5-dimethoxy-2'-chlorow4-sulfonic milgie-azobenzene.

acid-dimethyla Dn 4-amiuo-2,5-dimethoxy-2-sulfonic acid-diethylamide-4-nitroazobenzene.

-benzene Dull very greenishblue. -4chlorobenzene Violet-black.

-2-methy1-4-methoxy-benzene Blue-violet.

-6-methoxy-3.4-dichl0r0benzene Do. -2,4-dimethoxybenzene Do. -2-methylbenzene Reddishblack-blue.

-4-chlorobenzene Neutral black. -2-methyl-4-chloro-benzene Reddish black. -benzene D0.

-2-methylbenzene Do. -2methoxybenzene Do. -4-chlorobenzene Do. -2-methylA-methoxy-benzene Do.

-6-bromo-2A-dimethoxy-benzene D0. -6'-methoxy-3.4-dichloro-benzene Black Green ish black.

D -2-methylbenzene Do. Do imryben Pne Blue-black. D -4-chlor PM 1 Neutral black. 13 -2-metl1yl-4-chlorobenzene Greenish black. D0 maphthalnne Black. 4-amino2,5dimethoxy-2-nitro-4 sulfonic acid-dimethylamide- Neutral black.

azobenzene. v

D -2-methylbenzene Reddlsh black. D Q -2-methoxybenzene D0. 4-%mmo-2,5-diethoxy-2-sulfonic aoid-diethylam1de-4-n1tro-azo- -benzene Greenish black.

enzene.

D -2-methylbenzene Do. D -4-chloroh n m Do. D -3-nitrobenzene Do. Do manhthalene Black. Dn -2,4-dimethoxy-5-chlor ene Reddish black. Dn 2-(2,3-hydroxyna hthoyl-amino)-naphthalene Black. 4-amino-2, 5-d1methoxy-3-carboxylic acid-diethylam1de-4'- 4.4-di-(acetoacety amino)-3,3-d1methyl-diphenyl Orange-red.

chloroazobenzene. I 4-amino-2, 5dimethoxy-2-carboxylic acid-dimethylamidcd Bluish red.

4-nitroazobenzene. 4-amino-2, 5-dieth0xy-2-carboxylic acid-dimethylamide-4- do Bordeaux.

nitro-azobenzene. 4-amino-2, 5-dimethoxy-2-sulfonic acid-diethylamide 4-n1trodo Dark red-brown.

azobenzene. Y

1-(2.3-hydroxynaphthoyl-ammo)- 4-ammo-2, 5-d1methoxy-3-sulfonic acid-dimethylam1de-5-tr1- -2-methoxybenzene Blue-black.

fluoromethyl-azobenzene. 4-amino-2-methyl-5.5-dimethoxy-4-nitrilo-2-sulfonicacid-dle- -2-methylbenzene Deep current.

thylamide-azobenzene. s 4 amlno-amethyl-fi-ethoxy 5' methoxy-4'-nitrilo-2-sulionic '2-methoxybenzene Do.

acid-diethyl-amide-azobenzene. 4-amino-2, 5, 5-trimethoxy-4-nitri1o-2-sulfonic acid-diethyl- -2-methylbenzene Currant black.

amide-azobenzene. 4-amino-2, 5-diethoxy-5-mcth0xy-4-nitri1o-2-su1fonic acid- -4-chlorobenzene Do.

diethylamide-azobenzene.

XI l

wherein the azo-groups stand in para-position to each other, R and R1 stand for members of the 55 group consisting of radicals of the benzene and naphthalene series, X1 stands fo the group consisting of r a member of CeHs alkyl CaHl X: for a member of the group consisting of hydrogen, halogen and alkoxy and Z for a member of the group consisting of hydrogen, halogen and alkoxy, yielding, when produced on the fiber, gatrnet to black dyeings of good fastness proper res.

.. 2. Thewater-insolubleazo-dyestufis ofthe fol-u lowinggeneral formula: g A

and X3 for a member of the group consisting, of hydrogen, halogen and alkoxy; yielding, when produced on the fiber, garnet to black 'dyeings of good fastness properties,

3. The water-insoluble azo-dyestuflz of the following formula:

o11 on or yielding, when produced on thefiber, reddishblack dyeings of very good fastness to light,

chlorine and ironing;

4. Thewater-insoluble azordyestuff of the following formula: l

OCHt' win N N 'NO,

V JCONKMHB): Q .l l 7 H017 yielding, when produced on the fiber, blue-black dyeings of very good fastness to light, washing and chlorine.

5. Fiber dyed with the water-insoluble dyestufis as claimedin claim 1-. r r 6. Fiber dyed with; the water-insoluble dyestuffs as claimed in claim 2.

'7. Fiber dyed with the water-insoluble dyestuff as claimed in claim 3.

8. Fiber dyed with the water-insoluble dyestufi as claimed in claim 4.

9. The water-insolubleiazo dyestuff of there]- l n l e u a \c own-O yielding, when produced on the fiber, blue-black dyeingsof very good fastness-to light, washing and chlorine. v H

10. Fiber dyed with. the water-insolubleazodyestufi as claimed in c1aim'9.

ERWIN THQMA. I SEIDENFADEN. 

